Substituted oxime ethers and fungicides which contain these compounds

ABSTRACT

Substituted oxime ethers of the general formula ##STR1## where R 1  is alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, alkoxyalkyl, cycloalkyl, cycloalkylalkyl, cyanoalkyl, alkoxycarbonylalkyl, arylalkyl, heteroarylalkyl, arylalkenyl or aryloxyalkyl, the aromatic or heteroaromatic ring being substituted or unsubstituted, R 2  and R 3  are hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, halogen, cyano or nitro, R 4  is hydrogen, alkyl or aryl, the aromatic ring being substituted or unsubstituted, and X is CH or N, and fungicides containing these compounds.

The present invention relates to novel substituted oxime ethers and fungicides which contain these compounds.

The use of oxime ethers such as, for example, methyl 2-phenoxymethylphenylglyoxylate O-methyloxime as fungicides has been disclosed (EP 253,213). However, their fungicidal action is often inadequate.

We have now found that substituted oxime ethers of the general formula I ##STR2## where R¹ is C₁ -C₆ -alkyl, C₃ -C₆ -alkenyl, C₃ -C₁ -alkynyl, C₁ -C₆ -haloalkyl, C₃ -C₆ -haloalkenyl, C₁ -C₄ -alkoxy-C₁ -C₆ -alkyl, C₃ -C₆ -cycloalkyl, C₃ -C₆ -cycloalkyl-C₁ -C₄ -alkyl,cyano-C₁ -C₆ -alkyl, C₁ -C₆ -alkoxycarbonyl-C₁ -C₆ -alkyl, aryl-C₁ -C₆ -alkyl, heteroaryl-C₁ -C₆ -alkyl, aryl-C₃ -C₆ -alkenyl or aryloxy-C₁ -C₆ -alkyl, it being possible for the aromatic or heteroaromatic ring to be substituted by one or more of the following: C₁ -C₄ -alkyl, C₁ -C₂ -haloalkyl, C₃ -C₆ -cycloalkyl, C₁ -C₄ -alkoxy, C₁ -C₂ -haloalkoxy, halogen, aryl or aryloxy, R² and R³ are identical or different and are hydrogen, C₁ -C₄ -alkyl, C₁ -C₂ -haloalkyl, C₁ -C₄ -alkoxy, C₁ -C₂ -haloalkoxy, halogen, cyano or nitro, R⁴ is hydrogen, C₁ -C₆ -alkyl or aryl, it being possible for the aromatic ring to be substituted by one or more of the following: C₁ -C₄ -alkyl, C₁ -C₂ -haloalkyl, C₁ -C₄ -alkoxy, C₁ -C₂ -haloalkoxy, halogen, cyano or nitro, and X is CH or N, have an excellent fungicidal action which is better than that of the known oxime ethers.

Examples of possible meanings of the radicals in the general formula are:

R¹

C₁ -C₆ -alkyl (C₁ -C₄ -alkyl) (e.g. methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl, n-, iso-, sec-, tert- or neo-pentyl hexyl), C₃ -C₆ -alkenyl (e.g. allyl, 2-butenyl, 3-buteryl, 1-methyl-2-propenyl, 2-methyl-2-propenyl), C₃ -C₄ -alkynyl (e.g. propargyl, 2-butynyl), C₁ -C₆ -haloalkyl (e.g. 2-fluoroethyl), C₃ -C₆ -haloalkenyl (e.g. 3-chloroallyl), C₁ -C₄ -alkoxy-C₁ -C₆ -alkyl (e.g. 2-methoxyethyl, 3-ethoxypropyl), C₃ -C₆ -cycloalkyl (e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl), C₃ -C₆ -cycloalkyl-C₁ -C₄ -alkyl (e.g. cyclopropylmethyl, cyclohexylmethyl), cyano-C₁ -C₆ -alkyl (e.g. cyanomethyl, 3-cyanopropyl), C₁ -C₆ -alkoxy-carbonyl-C₁ -C₃ -alkyl (e.g. ethoxycarbonylmethyl, tert-butoxycarbonylmethyl, tert-butoxycarbonylpropyl), aryl-(phenyl)-C₁ -C₆ -alkyl (e.g. benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl), heteroaryl-(pyridyl, thienyl)-C₁ -C₆ -alkyl 3-pyridylmethyl, 2-thienylmethyl), aryl-(phenyl)-C₃ -C₆ -alkenyl (e.g.4-phenyl-2-butenyl, 4-phenyl-3 -butenyl), aryloxy-(phenoxy)-C₁ -C₆ -alkyl (e.g. phenoxymethyl, phenoxyethyl, phenoxypropyl, phenoxybutyl, naphthoxymethyl, naphthoxyethyl), it being possible for the aromatic (phenyl) or heteroaromatic (pyridyl, thienyl) ring to be substituted by one or more, e.g. 1 to 5, in particular 1 to 3, of the following:

C₁ -C₄ -alkyl (e.g. methyl, ethyl, propyl, butyl), C₁ -C₂ -haloalkyl (e.g. trifluoromethyl, trichloromethyl), C₃ -C₆ -cycloalkyl (e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl), C₁ -C₄ -alkoxy (e.g. methoxy, ethoxy, propoxy, butoxy), C₁ -C₂ -haloalkoxy (e.g. trifluoromethoxy), halogen (e.g. fluorine, chlorine, bromine), aryl (e.g. phenyl), aryloxy (e.g. phenoxy),

R² and R³, which can be identical or different, hydrogen, C₁ -C₄ -alkyl (e.g. methyl, ethyl, n- or isopropyl, butyl), C₁ -C₂ -haloalkyl (e.g. trifluoromethyl, trichloromethyl), C₁ -C₄ -alkoxy (e.g. methoxy, ethoxy, n- or iso-propoxy, butoxy), C₁ -C₂ -haloalkoxy (e.g. trifluoromethoxy), halogen (e.g. fluorine, chlorine, bromine, iodine), cyano or nitro, R⁴

C₁ -C₆ alkyl (C₁ -C₄ -alkyl) (e.g. methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl, n-, iso-, sec-, tert- or neo-pentyl, hexyl) or aryl (e.g. phenyl), it being possible for the aromatic ring to be substituted by one or more, e.g. 1 to 5, in particular 1 to 3, of the following: C₁ -C₄ -alkyl (e.g. methyl, ethyl, propyl, butyl), C₁ -C₂ -haloalkyl (e.g. trifluoromethyl, trichloromethyl), C₁ -C₄ -alkoxy (e.g. methoxy, ethoxy, propoxy, butoxy), C₁ -C₂ -haloalkoxy(e.g.difluoromethoxy,trifluoromethoxy),halogen (e.g. fluorine, chlorine, bromine, iodine),cyano or nitro, X CH or N.

The radical --C(R⁴)═N--O--R¹ on the phenyl can be in the 2 or, preferably, in the 3 or 4 position with respect to the --O--CH₂ -- radical.

Because of the C═C and C═N double bonds, preparation of the novel compounds of the general formula I may result in mixtures of E and Z isomers. These can be separated in a conventional manner, e.g. by crystallization or chromatography. The present invention relates both to the individual isomeric compounds and to mixtures thereof, and all of them can be used as fungicides. With regard to the --C(COOCH₃)═X--OCH₃ group, preferred compounds have the E configuration of the COOCH₃ and OCH₂ on the C═X double bond. With regard to the --C(R⁴)═N--OR¹ group, preferred compounds have the Z configuration of R⁴ and OR¹ on the C═N double bond

The novel compounds of the general formula I as claimed in claim 1 are prepared, for example, in such a way that a substituted oxime ether of the general formula II is reacted with a substituted benzyl compound of the general formula III where Y is a leaving group (e.g. chloride, bromide, p-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate). ##STR3## R¹, R², R², R⁴ and X have the abovementioned meanings.

These reactions can be carried out, for example, in an inert solvent or diluent (e.g. acetone, acetonitrile, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, N,N'-dimethylpropyleneurea or pyridine), using a base (e.g. sodium carbonate, potassium carbonate). It may also be advantageous to add a catalyst such as tris(3,6-dioxoheptyl)amine to the reaction mixture.

An alternative procedure is such that the compounds of the general formula II are initially converted with a base (e.g. sodium hydroxide, potassium hydroxide, sodium methanolate) into the corresponding sodium or potassium phenolates, and the latter are then reacted in an inert solvent or diluent (e.g. dimethylformamide) with the substituted benzyl compounds of the general formula III to give the compounds of the formula I according to the invention.

These reactions can also be carried out in a two-phase system (e.g. carbon tetrachloride/water). Examples of suitable phase-transfer catalysts are trioctylpropylammonium chloride or cetyltrimethylammonium chloride.

The substituted oxime ethers of the formula II required to prepare the novel compounds of the general formula I are either known or can be prepared by conventional processes.

Also required for the preparation of the compounds of the generally formula I according to the invention are the substituted benzyl compounds of the general formula III. Compounds of the general formula IIIa (X=N, Y=chloride, bromide) are obtained by halogenation of methyl 2-methylphenylglyoxylate O-methyloxime IV by literature methods. This is achieved, for example, with bromine or chlorine in an inert solvent (e.g. tetrachloromethane), with or without irradiation from a light source (e.g. Hg vapor lamp, 300W) or by reaction with N-chloro- or N-bromosuccinide (cf. Horner, Winkelmann, Angew. Chem. 71 (1959) 349). ##STR4##

Methyl 2-methylphenylglyoxylate O-methyloxime IV can be prepared by reacting methyl 2-methylphenylglyoxylate V for example a) with O-methylhydroxylamine hydrochloride or b) with hydroxylamine hydrochloride to give the corresponding oxime and reacting the latter with a methylating agent of the formula CH₃ -L where L is a leaving group (e.g. chloride, bromide, iodide, methylsulfate) (cf. DE 3,623,921). ##STR5##

Benzyl halides of the generally formula IIIa (X=N, Y=chloride, bromide) are also obtained when methyl 2-halomethylphenylglyoxylates of the formula VI (Y=chloride, bromide) are reacted a) with O-methylhydroxylamine hydrochloride or b) with hydroxylamine hydrochloride to give the corresponding oxime and reacting the latter with a methylating agent of the formula CH₃ -L where L is a leaving group (e.g. chloride, bromide, iodide, methylsulfate) (cf. DE 3,623,921). ##STR6##

Methyl 2-halomethylphenylglyoxylates of the formula VI (Y =chloride, bromide) can be prepared by halogenating methyl 2-methylphenylglyoxylate V by literature methods. The reaction is carried out, for example, with bromine or chlorine in an inert solvent (e.g. tetrachloromethane) with or without irradiation from a light source (e.g. Hg vapor lamp, 300 W) or with N-chloro- or N-bromosuccinimide (cf. Horner, Winkelmann, Angew. Chem. 71 (1959) 349). ##STR7##

Substituted benzyl compounds of the general formula IIIb (X=CH, Y =chloride, bromide) are either known or can be prepared by conventional processes. Appropriate methods of preparation are described, for example, in DE 3,519,280, DE 3,545,318 and DE 3,545,319.

Substituted benzyl compounds of the general formula IIIc (X=CH or N, Y=p-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate) can be prepared from the corresponding compounds of the general formula IIIa (X=N, Y=chloride, bromide) or IIIb (X=CH, Y=chloride, bromide) by reaction with p-toluenesulfonic acid (Y=p-toluenesulfonate), methanesulfonic acid (Y=methanesulfonate) or trifluoromethanesulfonic acid (Y=trifluoromethanesulfonate). The reactions can be carried out, for example, in an inert solvent or diluent (e.g. dimethylformamide) in the presence of a base (e.g. potassium carbonate). An alternative procedure is such that the appropriate sulfonic acid is initially converted into a sodium or potassium salt and the latter is then reacted in an inert solvent or diluent (e.g. dimethylformamide) with a compound of the general formula IIIa or IIIb to give the substituted benzyl compounds of the general formula IIIc.

The novel compounds of the general formula I can also be prepared by reacting the novel substituted carbonyl compounds of the general formula VII with a substituted hydroxylamine of the general formula VIII or with an acid addition salt (e.g. hydrochloride, hydrobromide) of VIII. ##STR8## R¹, R², R³, R⁴ and X have the abovementioned meanings.

The reaction can be carried out in an inert solvent or diluent (e.g. methanol, ethanol, toluene) or in a two-phase system (e.g. toluene/water). It may also be advantageous to add a base (e.g. triethylamine, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide) to the reaction mixture.

The novel carbonyl compounds of the general formula VII are required as starting compounds. These are obtained by reacting the substituted benzyl compounds of the general formula III where Y is a leaving group (e.g. chloride, bromide, p-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate) with substituted carbonyl compounds of the general formula IX. The compounds of the general formula IX are known. They can be prepared by conventional processes. ##STR9## R¹, R², R³, R⁴ and X have the abovementioned meanings.

The examples and procedures which follow are intended to illustrate the preparation of the novel active ingredients and their precursors.

PROCEDURE 1 Methyl 2-bromomethylphenylglyoxylate O-methyloxime

21.4 g (0.133 mol) of bromine are added to a stirred solution of 27.5 g (0.133 mol) of methyl 2-methylphenylglyoxylate O-methyloxime in 400 ml of tetrachloromethane. The mixture is then refluxed while irradiating with a 300W Hg vapor lamp for four hours. It is then concentrated, the residue is taken up in ethyl acetate/water, and the organic phase is washed with H₂ O, dried with sodium sulfate and evaporated. The crude product is purified by chromatography on silica gel with cyclohexane/ethyl acetate (9/1). 17.4 g (46%) of the abovementioned compound are obtained as an oil.

EXAMPLE 1 Methyl 2-(2-methoxyiminomethylphenoxymethyl)phenylglyoxylate O-methyloxime

3.0 g (20 mmol) of 2-hydroxybenzaldehyde O-methyloxime are dissolved in 20 ml of methanol, and 3.6 g (20 mmol) of sodium methanolate (30% strength in methanol) are added. The mixture is refluxed for four hours and then concentrated. The residue is taken up in 100 ml of dimethylformamide, and 6.5 g (23 mmol) of methyl 2-bromomethylphenylglyoxylate O-methyloxime in 50 ml of dimethylformamide are added. The mixture is stirred at 100° C. for 5 hours, the solvent is stripped off, and the residue is taken up in ethyl acetate. The organic phase is washed with water, dried and concentrated. The residue is triturated with pentane to induce crystallization. 4.8 g (67% of theory) of the title compound are obtained in the form of colorless crystals (melting point 73°-76° C., compound no. 2).

EXAMPLE 2 Methyl α-[2-(2-ethoxyiminomethylphenoxymethyl)phenyl]-β-methoxyacrylate

6.9 g (42 mmol) of 2-hydroxybenzaldehyde O-ethyloxime and 10.0 g (35 mmol) of methyl α-(2-bromometnylphenyl)-β-methoxyacrylate are dissolved in 100 ml of dimethylformamide, and 7.3 g (53 mmol) of potassium carbonate are added. The mixture is stirred at room temperature for 48 hours and then concentrated, and the residue is taken up in methylene chloride. The organic phase is washed with water, dried over MgSO₄ and concentrated. The resulting oil is purified by chromatography on silica gel (cyclohexane/ethyl acetate). 8.4 g (65% of theory) of the title compound are obtained in the form of colorless crystals (melting point 86°-88° C., compound no. 23).

EXAMPLE 3 Methyl α-[2-(3-(1-ethoxyiminoethyl)phenoxymethyl)phenyl]-βmethoxycarylate

7.5 g (0.042 mol) of 3-(1-ethyoxyiminoethyl)phenol and 10.0 g (0.035 mol) methyl α-(2-bromomethylphenyl)-β-methoxyacrylate are dissolved in 100 ml of dimethylformamide, and 7.3 (0.053 mol) of potassium carbonate are added. The mixture is stirred at room temperature (20° C.) for 48 hours, hydrolyzed with water and extracted with diethyl ether. The organic phase is washed with water, dried over magnesium sulfate and concentrated. The resulting oil is purified by chromatography on alumina (cyclohexane). 7.3 g (54%) of the title compound are obtained as a colorless oil (compound no. 447).

EXAMPLE 4 Methyl 2-[3-(1-n-butoxyiminoethyl)phenoxymethyl]phenylglyoxylate O-methyloxime

a) 3.0 g (0.022 mol) of 3-hydroxyacetophenone and 6.0 g (0.021 mol) of methyl 2-bromomethylphenylglyoxylate O-methyloxime are dissolved in 30 ml of dimethylformamide, and 5.5 g (0.040 yol) of potassium carbonate are added. The mixture is stirred at room temperature for 24 hours, hydrolyzed with water and extracted with methyl tert-butyl ether. The organic phase is washed with water, dried and concentrated. 5.8 g (85%) of methyl 2-(3-acetylphenoxymethyl)phenylglyoxylate O-methyloxime are obtained as a colorless oil.

5.8 g (0.017 mol) of methyl 2-(3-acetylphenoxymethyl)phenylglyoxylate O-methyloxime and 2.5 g (0.020 mol) of n-butoxyamine hydrochloride in 60 ml of methanol are stirred at room temperature for 24 hours. The mixture is then hydrolyzed with water and extracted with methyl tert-butyl ether. The organic phase is washed with water, dried and concentrated. 5.0 g (71%) of the title compound are obtained as a colorless oil (compound no. 470).

EXAMPLE 5 Methyl 2-[4-(1-benzyloxyiminoethyl)phenoxymethyl]phenylglyoxylate O-methyloxime

a) 3.0 g (0.022 mol) of 4-hydroxyacetophenone and 6.0 g (0.021 mol) of methyl 2-bromomethylphenylglyoxylate O-methyloxime are dissolved in 30 ml of dimethylformamide, and 5.5 g (0.040 mol) of potassium carbonate are added. The mixture is stirred at room temperature for 24 hours, hydrolyzed with water and extracted with methyl tert-butyl ether. The organic phase is washed with water, dried and concentrated. 5.3 g (78%) of methyl 2-(4-acetylphenoxymethyl)phenylglyoxylate O-methyloxime are obtained as a colorless oil.

b) 5.3 g (0.016 mol) of methyl 2-(4-acetylphenoxymethyl)phenylglyoxylate O-methyloxime and 3.0 g (0.019 mol) of benzyloxyamine hydrochloride in 60 ml of methanol are stirred at room temperature for 24 hours. The mixture is then hydrolyzed with water and extracted with methyl tert-butyl ether. The organic phase is washed with water, dried and concentrated. 5.9 g (83%) of the title compound are obtained in the form of colorless crystals (melting point 104°-106° C., compound no. 590).

The compounds listed in Tables 1 to 3 can be prepared in a corresponding manner.

                                      TABLE 1                                      __________________________________________________________________________     Compounds of the general formula Ia (2-position of the oxime ether). The       configuration statement                                                        (E) relates to the methyl β-methoxyacrylate group or the methyl           glyoxylate O-methyloxime group.                                                 ##STR10##                                    Ia                               Comp. no.                                                                            R.sup.1             R.sup.2                                                                             R.sup.3                                                                            R.sup.4                                                                            X   mp. (°C.)                    __________________________________________________________________________      1    CH.sub.3            H    H   H   CH  82-84 (E)                            2    CH.sub.3            H    H   H   N   73-76 (E)                            3    CH.sub.3            4-Cl H   H   CH                                       4    CH.sub.3            4-Cl H   H   N                                        5    CH.sub.3            4-CH.sub.3                                                                          H   H   CH                                       6    CH.sub.3            4-CH.sub.3                                                                          H   H   N                                        7    CH.sub.3            4-OCH.sub.3                                                                         H   H   CH                                       8    CH.sub.3            4-OCH.sub.3                                                                         H   H   N                                        9    CH.sub.3            5-F  H   H   CH                                       10   CH.sub.3            5-F  H   H   N                                        11   CH.sub.3            5-Cl H   H   CH                                       12   CH.sub.3            5-Cl H   H   N                                        13   CH.sub.3            5-Br H   H   CH                                       14   CH.sub.3            5-Br H   H   N                                        15   CH.sub.3            5-CH.sub.3                                                                          H   H   CH                                       16   CH.sub.3            5-CH.sub.3                                                                          H   H   N                                        17   CH.sub.3            5-OCH.sub.3                                                                         H   H   CH                                       18   CH.sub.3            5-OCH.sub.3                                                                         H   H   N                                        19   CH.sub.3            6-OCH.sub.3                                                                         H   H   CH                                       20   CH.sub.3            6-OCH.sub.3                                                                         H   H   N                                        21   CH.sub.3            4-Cl 6-Cl                                                                               H   CH                                       22   CH.sub.3            4-Cl 6-Cl                                                                               H   N                                        23   CH.sub.3CH.sub.2    H    H   H   CH  86-88 (E)                            24   CH.sub.3CH.sub.2    H    H   H   N   89-90 (E)                            25   CH.sub.3CH.sub.2    4-Cl H   H   CH  95-97 (E)                            26   CH.sub.3CH.sub.2    4-Cl H   H   N                                        27   CH.sub.3CH.sub.2    4-CH.sub.3                                                                          H   H   CH                                       28   CH.sub.3CH.sub.2    4-CH.sub.3                                                                          H   H   N                                        29   CH.sub.3CH.sub.2    4-OCH.sub.3                                                                         H   H   CH                                       30   CH.sub.3CH.sub.2    4-OCH.sub.3                                                                         H   H   N                                        31   CH.sub.3CH.sub.2    5-F  H   H   CH                                       32   CH.sub.3CH.sub.2    5-F  H   H   N                                        33   CH.sub.3CH.sub.2    5-Cl H   H   CH                                       34   CH.sub.3CH.sub.2    5-Cl H   H   N                                        35   CH.sub.3CH.sub.2    5-Br H   H   CH                                       36   CH.sub.3CH.sub.2    5-Br H   H   N                                        37   CH.sub.3CH.sub.2    5-CH.sub.3                                                                          H   H   CH                                       38   CH.sub.3CH.sub.2    5-CH.sub.3                                                                          H   H   N                                        39   CH.sub.3CH.sub.2    5-OCH.sub.3                                                                         H   H   CH                                       40   CH.sub.3CH.sub.2    5-OCH.sub.3                                                                         H   H   N                                        41   CH.sub.3CH.sub.2    6-OCH.sub.3                                                                         H   H   CH                                       42   CH.sub.3CH.sub.2    6-OCH.sub.3                                                                         H   H   N                                        43   CH.sub.3CH.sub.2    4-Cl 6-Cl                                                                               H   CH                                       44   CH.sub.3CH.sub.2    4-Cl 6-Cl                                                                               H   N                                        45   CH.sub.3CH.sub.2 CH.sub.2                                                                          H    H   H   CH                                       46   CH.sub.3CH.sub.2CH.sub.2                                                                           H    H   H   N                                        47   CH.sub.2CHCH.sub.2  H    H   H   CH                                       48   CH.sub.2CHCH.sub.2  H    H   H   N                                        49   CH.sub.3CH(CH.sub.3)                                                                               H    H   H   CH                                       50   CH.sub.3CH(CH.sub.3)                                                                               H    H   H   N                                        51   HCCCH.sub.2         H    H   H   CH                                       52   HCCCH.sub.2         H    H   H   N                                        53   cyclo-C.sub.3 H.sub.5CH.sub.2                                                                      H    H   H   CH                                       54   cyclo-C.sub.3 H.sub.5CH.sub.2                                                                      H    H   H   N                                        55   CH.sub.3CH.sub.2CH.sub.2CH.sub.2                                                                   H    H   H   CH                                       56   CH.sub.3CH.sub.2CH.sub.2CH.sub.2                                                                   H    H   H   N                                        57   CH.sub.3CHCHCH.sub.2                                                                               H    H   H   CH                                       58   CH.sub.3CHCHCH.sub.2                                                                               H    H   H   N                                        59   CH.sub.3(CH.sub.2).sub.5                                                                           H    H   H   CH                                       60   CH.sub.3(CH.sub.2).sub.5                                                                           H    H   H   N                                        61   cyclo-C.sub.6 H.sub.11                                                                             H    H   H   CH                                       62   cyclo-C.sub.6 H.sub.11                                                                             H    H   H   N                                        63   C.sub.6 H.sub.5CH.sub.2                                                                            H    H   H   CH                                       64   C.sub.6 H.sub.5CH.sub.2                                                                            H    H   H   N                                        65   4-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H   H   CH                                       66   4-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H   H   N                                        67   3-CF.sub.3C.sub.6 H.sub.4CH.sub.2                                                                  H    H   H   CH                                       68   3-CF.sub.3C.sub.6 H.sub.4CH.sub.2                                                                  H    H   H   N                                        69   4-ClC.sub.6 H.sub.4CH.sub.2CH.sub.2                                                                H    H   H   CH                                       70   4-ClC.sub.6 H.sub.4CH.sub.2CH.sub.2                                                                H    H   H   N                                        71   C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2                                                            H    H   H   CH                                       72   C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2                                                            H    H   H   N                                        73   C.sub.6 H.sub.5(CH.sub.2).sub.4                                                                    H    H   H   CH                                       74   C.sub.6 H.sub.5(CH.sub.2).sub.4                                                                    H    H   H   N                                        75   C.sub.6 H.sub.5CH.sub.2CHCHCH.sub.2                                                                H    H   H   CH                                       76   C.sub.6 H.sub.5CH.sub.2CHCHCH.sub.2                                                                H    H   H   N                                        77   4-FC.sub.6 H.sub.4CHCHCH.sub.2CH.sub.2                                                             H    H   H   CH                                       78   4-FC.sub.6 H.sub.4CHCHCH.sub.2CH.sub.2                                                             H    H   H   N                                        79   t-C.sub.4 H.sub.9 OCOCH.sub.2                                                                      H    H   H   CH                                       80   t-C.sub.4 H.sub.9 OCOCH.sub.2                                                                      H    H   H   N                                        81   t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3                                                              H    H   H   CH                                       82   t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3                                                              H    H   H   N                                        83   ClCHCHCH.sub.2      H    H   H   CH                                       84   ClCHCHCH.sub.2      H    H   H   N                                       221   C.sub.2 H.sub.5     6-OC.sub.2 H.sub.5                                                                  H   H   CH                                      222   C.sub.2 H.sub.5     6-OC.sub.2 H.sub.5                                                                  H   H   N                                       223   CH.sub. 3C(CH.sub.3).sub.2                                                                         H    H   H   CH                                      224   CH.sub.3C(CH.sub.3).sub.2                                                                          H    H   H   N                                       225   CH.sub.3CH(CH.sub.3)CH.sub.2                                                                       H    H   H   CH                                      226   CH.sub.3CH(CH.sub.3)CH.sub.2                                                                       H    H   H   N                                       227   CH.sub.2C(CH.sub.3)CH.sub.2                                                                        H    H   H   CH                                      228   CH.sub.2C(CH.sub.3)CH.sub.2                                                                        H    H   H   N                                       229   CH.sub.3CH(CH.sub.3)CH.sub.2CH.sub.2                                                               H    H   H   CH                                      230   CH.sub.3CH(CH.sub.3)CH.sub.2CH.sub.2                                                               H    H   H   N                                       231   CH.sub.3(CH.sub.2).sub.4                                                                           H    H   H   CH                                      232   CH.sub.3(CH.sub.2).sub.4                                                                           H    H   H   N                                       233   2-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H   H   CH                                      234   2-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H   H   N                                       235   3-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H   H   CH                                      236   3-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H   H   N                                       237   2-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H   H   CH                                      238   2-ClC.sub.6 H.sub.4CH.sub. 2                                                                       H    H   H   N                                       239   3,4-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H   H   CH                                      240   3,4-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H   H   N                                       241   2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H   H   CH                                      242   2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H   H   N                                       243   C.sub.6 H.sub.5CH.sub.2CH.sub.2                                                                    H    H   H   CH                                      244   C.sub.6 H.sub.5CH.sub.2CH.sub.2                                                                    H    H   H   N                                       245   C.sub.6 H.sub.5CHCHCH.sub.2CH.sub.2                                                                H    H   H   CH                                      246   C.sub.6 H.sub.5CHCHCH.sub.2CH.sub.2                                                                H    H   H   N                                       247   4-ClC.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                            H    H   H   CH                                      248   4-ClC.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                            H    H   H   N                                       249   4-CF.sub.3C.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                      H    H   H   CH                                      250   4-CF.sub.3C.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                      H    H   H   N                                       311   CH.sub.3            H    H   CH.sub.3                                                                           CH                                      312   CH.sub.3            H    H   CH.sub.3                                                                           N                                       313   CH.sub.3            4-Cl H   CH.sub.3                                                                           CH                                      314   CH.sub.3            4-Cl H   CH.sub.3                                                                           N                                       315   CH.sub.3            4-CH.sub.3                                                                          H   CH.sub.3                                                                           CH                                      316   CH.sub.3            4-CH.sub.3                                                                          H   CH.sub.3                                                                           N                                       317   CH.sub.3            4-OCH.sub.3                                                                         H   CH.sub.3                                                                           CH                                      318   CH.sub.3            4-OCH.sub.3                                                                         H   CH.sub.3                                                                           N                                       319   CH.sub.3            5-F  H   CH.sub.3                                                                           CH                                      320   CH.sub.3            5-F  H   CH.sub.3                                                                           N                                       321   CH.sub.3            5-Cl H   CH.sub.3                                                                           CH                                      322   CH.sub.3            5-Cl H   CH.sub.3                                                                           N                                       323   CH.sub.3            5-Br H   CH.sub.3                                                                           CH                                      324   CH.sub.3            5-Br H   CH.sub.3                                                                           N                                       325   CH.sub.3            5-CH.sub.3                                                                          H   CH.sub.3                                                                           CH                                      326   CH.sub.3            5-CH.sub.3                                                                          H   CH.sub.3                                                                           N                                       327   CH.sub.3            5-OCH.sub.3                                                                         H   CH.sub.3                                                                           CH                                      328   CH.sub.3            5-OCH.sub.3                                                                         H   CH.sub.3                                                                           N                                       329   CH.sub.3            6-OCH.sub.3                                                                         H   CH.sub.3                                                                           CH                                      330   CH.sub.3            6-OCH.sub.3                                                                         H   CH.sub.3                                                                           N                                       331   CH.sub.3            4-Cl 6-Cl                                                                               CH.sub.3                                                                           CH                                      332   CH.sub.3            4-Cl 6-Cl                                                                               CH.sub.3                                                                           N                                       333   CH.sub.3CH.sub.2    H    H   CH.sub.3                                                                           CH                                      334   CH.sub.3CH.sub.2    H    H   CH.sub.3                                                                           N                                       335   CH.sub. 3CH.sub.2   4-Cl H   CH.sub.3                                                                           CH                                      336   CH.sub.3CH.sub.2    4-Cl H   CH.sub.3                                                                           N                                       337   CH.sub.3CH.sub.2    4-CH.sub.3                                                                          H   CH.sub.3                                                                           CH                                      338   CH.sub.3CH.sub.2    4-CH.sub.3                                                                          H   CH.sub.3                                                                           N                                       339   CH.sub.3CH.sub.2    4-OCH.sub.3                                                                         H   CH.sub.3                                                                           CH                                      340   CH.sub.3CH.sub.2    4-OCH.sub.3                                                                         H   CH.sub.3                                                                           N                                       341   CH.sub.3CH.sub.2    5-F  H   CH.sub.3                                                                           CH                                      342   CH.sub.3CH.sub.2    5-F  H   CH.sub.3                                                                           N                                       343   CH.sub.3CH.sub.2    5-Cl H   CH.sub.3                                                                           CH                                      344   CH.sub.3CH.sub.2    5-Cl H   CH.sub.3                                                                           N                                       345   CH.sub.3CH.sub.2    5-Br H   CH.sub.3                                                                           CH                                      346   CH.sub.3CH.sub.2    5-Br H   CH.sub.3                                                                           N                                       347   CH.sub.3CH.sub.2    5-CH.sub.3                                                                          H   CH.sub.3                                                                           CH                                      348   CH.sub.3CH.sub.2    5-CH.sub.3                                                                          H   CH.sub.3                                                                           N                                       349   CH.sub.3CH.sub.2    5-OCH.sub.3                                                                         H   CH.sub.3                                                                           CH                                      350   CH.sub.3CH.sub.2    5-OCH.sub.3                                                                         H   CH.sub.3                                                                           N                                       351   CH.sub.3CH.sub.2    6-OCH.sub.3                                                                         H   CH.sub.3                                                                           CH                                      352   CH.sub.3CH.sub.2    6-OCH.sub.3                                                                         H   CH.sub.3                                                                           N                                       353   CH.sub.3CH.sub.2    4-Cl 6-Cl                                                                               CH.sub.3                                                                           CH                                      354   CH.sub. 3CH.sub.2   4-Cl 6-Cl                                                                               CH.sub.3                                                                           N                                       355   CH.sub.3CH.sub.2CH.sub.2                                                                           H    H   CH.sub.3                                                                           CH                                      356   CH.sub.3CH.sub.2CH.sub.2                                                                           H    H   CH.sub.3                                                                           N                                       357   CH.sub.2CHCH.sub.2  H    H   CH.sub.3                                                                           CH                                      358   CH.sub.2CHCH.sub.2  H    H   CH.sub.3                                                                           N                                       359   CH.sub.3CH(CH.sub.3)                                                                               H    H   CH.sub.3                                                                           CH                                      360   CH.sub.3CH(CH.sub.3)                                                                               H    H   CH.sub.3                                                                           N                                       361   HCCCH.sub.2         H    H   CH.sub.3                                                                           CH                                      362   HCCCH.sub.2         H    H   CH.sub.3                                                                           N                                       363   cyclo-C.sub.3 H.sub.5CH.sub.2                                                                      H    H   CH.sub.3                                                                           CH                                      364   cyclo-C.sub.3 H.sub.5CH.sub.2                                                                      H    H   CH.sub.3                                                                           N                                       365   CH.sub.3CH.sub.2CH.sub.2CH.sub.2                                                                   H    H   CH.sub.3                                                                           CH                                      366   CH.sub.3CH.sub.2CH.sub.2CH.sub.2                                                                   H    H   CH.sub.3                                                                           N                                       367   CH.sub.3CHCHCH.sub.2                                                                               H    H   CH.sub.3                                                                           CH                                      368   CH.sub.3CHCHCH.sub.2                                                                               H    H   CH.sub.3                                                                           N                                       369   CH.sub.3(CH.sub.2).sub.5                                                                           H    H   CH.sub. 3                                                                          CH                                      370   CH.sub.3(CH.sub.2).sub.5                                                                           H    H   CH.sub.3                                                                           N                                       371   cyclo-C.sub.6 H.sub.11                                                                             H    H   CH.sub.3                                                                           CH                                      372   cyclo-C.sub.6 H.sub.11                                                                             H    H   CH.sub.3                                                                           N                                       373   C.sub.6 H.sub.5CH.sub.2                                                                            H    H   CH.sub.3                                                                           CH                                      374   C.sub.6 H.sub.5CH.sub.2                                                                            H    H   CH.sub.3                                                                           N                                       375   4-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H   CH.sub.3                                                                           CH                                      376   4-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H   CH.sub.3                                                                           N                                       377   3-CF.sub.3C.sub.6 H.sub.4CH.sub.2                                                                  H    H   CH.sub.3                                                                           CH                                      378   3-CF.sub.3C.sub.6 H.sub.4CH.sub.2                                                                  H    H   CH.sub.3                                                                           N                                       379   4-ClC.sub.6 H.sub.4CH.sub.2CH.sub.2                                                                H    H   CH.sub.3                                                                           CH                                      380   4-ClC.sub.6 H.sub.4CH.sub.2CH.sub.2                                                                H    H   CH.sub.3                                                                           N                                       381   C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2                                                            H    H   CH.sub.3                                                                           CH                                      382   C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2                                                            H    H   CH.sub.3                                                                           N                                       383   C.sub.6 H.sub.5(CH.sub.2).sub.4                                                                    H    H   CH.sub.3                                                                           CH                                      384   C.sub.6 H.sub.5(CH.sub.2).sub.4                                                                    H    H   CH.sub. 3                                                                          N                                       385   C.sub.6 H.sub.5CH.sub.2CHCHCH.sub.2                                                                H    H   CH.sub.3                                                                           CH                                      386   C.sub.6 H.sub.5CH.sub.2CHCHCH.sub.2                                                                H    H   CH.sub.3                                                                           N                                       387   4-FC.sub.6 H.sub.4CHCHCH.sub.2CH.sub.2                                                             H    H   CH.sub.3                                                                           CH                                      388   4-FC.sub.6 H.sub.4CHCHCH.sub.2CH.sub.2                                                             H    H   CH.sub.3                                                                           N                                       389   t-C.sub.4 H.sub.9 OCOCH.sub.2                                                                      H    H   CH.sub.3                                                                           CH                                      390   t-C.sub.4 H.sub.9 OCOCH.sub.2                                                                      H    H   CH.sub.3                                                                           N                                       391   t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3                                                              H    H   CH.sub.3                                                                           CH                                      392   t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3                                                              H    H   CH.sub.3                                                                           N                                       393   ClCHCHCH.sub.2      H    H   CH.sub.3                                                                           CH                                      394   ClCHCHCH.sub.2      H    H   CH.sub.3                                                                           N                                       395   C.sub.2 H.sub.5     6-OC.sub.2 H.sub.5                                                                  H   CH.sub.3                                                                           CH                                      396   C.sub.2 H.sub.5     6-OC.sub.2 H.sub.5                                                                  H   CH.sub.3                                                                           N                                       397   CH.sub.3C(CH.sub.3).sub.2                                                                          H    H   CH.sub.3                                                                           CH                                      398   CH.sub.3C(CH.sub.3).sub.2                                                                          H    H   CH.sub.3                                                                           N                                       399   CH.sub.3CH(CH.sub.3)CH.sub.2                                                                       H    H   CH.sub.3                                                                           CH                                      400   CH.sub.3CH(CH.sub.3)CH.sub.2                                                                       H    H   CH.sub.3                                                                           N                                       401   CH.sub.2C(CH.sub.3)CH.sub.2                                                                        H    H   CH.sub.3                                                                           CH                                      402   CH.sub.2C(CH.sub.3)CH.sub.2                                                                        H    H   CH.sub.3                                                                           N                                       403   CH.sub.3CH(CH.sub.3)CH.sub.2CH.sub.2                                                               H    H   CH.sub.3                                                                           CH                                      404   CH.sub.3CH(CH.sub.3)CH.sub.2CH.sub.2                                                               H    H   CH.sub.3                                                                           N                                       405   CH.sub.3(CH.sub.2).sub.4                                                                           H    H   CH.sub.3                                                                           CH                                      406   CH.sub.3(CH.sub.2).sub.4                                                                           H    H   CH.sub.3                                                                           N                                       407   2-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H   CH.sub.3                                                                           CH                                      408   2-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H   CH.sub.3                                                                           N                                       409   3-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H   CH.sub.3                                                                           CH                                      410   3-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H   CH.sub.3                                                                           N                                       411   2-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H   CH.sub.3                                                                           CH                                      412   2-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H   CH.sub.3                                                                           N                                       413   3,4-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H   CH.sub.3                                                                           CH                                      414   3,4-Cl.sub. 2C.sub.6 H.sub.3CH.sub.2                                                               H    H   CH.sub.3                                                                           N                                       415   2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H   CH.sub.3                                                                           CH                                      416   2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H   CH.sub.3                                                                           N                                       417   C.sub.6 H.sub.5CH.sub.2CH.sub.2                                                                    H    H   CH.sub.3                                                                           CH                                      418   C.sub.6 H.sub.5CH.sub.2CH.sub.2                                                                    H    H   CH.sub.3                                                                           N                                       419   C.sub.6 H.sub.5CHCHCH.sub.2CH.sub.2                                                                H    H   CH.sub.3                                                                           CH                                      420   C.sub.6 H.sub.5CHCHCH.sub.2CH.sub.2                                                                H    H   CH.sub.3                                                                           N                                       421   4-ClC.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                            H    H   CH.sub.3                                                                           CH                                      422   4-ClC.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                            H    H   CH.sub.3                                                                           N                                       423   4-CF.sub.3C.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                      H    H   CH.sub.3                                                                           CH                                      424   4-CF.sub.3C.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                      H    H   CH.sub.3                                                                           N                                       425   CH.sub.3            H    H   C.sub.6 H.sub.5                                                                    CH                                      426   CH.sub.3            H    H   C.sub.6 H.sub.5                                                                    N                                       427   C.sub.2 H.sub.5     H    H   C.sub.6 H.sub. 5                                                                   CH                                      428   C.sub.2 H.sub.5     H    H   C.sub.6 H.sub.5                                                                    N                                       429   CH.sub.3CH.sub.2CH.sub.2                                                                           H    H   CH                                          430   CH.sub.3CH.sub.2CH.sub.2                                                                           H    H   C.sub.6 H.sub.5                                                                    N                                       431   CH.sub.3(CH.sub.2).sub.5                                                                           H    H   C.sub.6 H.sub.5                                                                    CH                                      432   CH.sub.3(CH.sub.2).sub.5                                                                           H    H   C.sub.6 H.sub.5                                                                    N                                       433   C.sub.6 H.sub.5CH.sub.2                                                                            H    H   C.sub.6 H.sub.5                                                                    CH                                      434   C.sub.6 H.sub.5CH.sub.2                                                                            H    H   C.sub.6 H.sub.5                                                                    N                                       __________________________________________________________________________

                                      TABLE 2                                      __________________________________________________________________________     Compounds of the general formula Ib (3-position of the oxime ether).           The configuration statement relates to the                                     methyl β-methoxyacrylate group or the methyl glyoxylate                   O-methyloxime group.                                                            ##STR11##                                  Ib                                 Comp. no.                                                                            R.sup.1             R.sup.2                                                                             R.sup.3                                                                           R.sup.4                                                                           X  mp. (°C.)                       __________________________________________________________________________      85   CH.sub.3            H    H  H  CH  75-77 (E)                              86   CH.sub.3            H    H  H  N  oil (E)                                 87   CH.sub.3            2-Cl 5-Cl                                                                              H  CH                                         88   CH.sub.3            2-Cl 5-Cl                                                                              H  N                                          89   CH.sub.3            4-Cl H  H  CH                                         90   CH.sub.3            4-Cl H  H  N                                          91   CH.sub.3            4-CH.sub.3                                                                          H  H  CH                                         92   CH.sub.3            4-CH.sub.3                                                                          H  H  N                                          93   CH.sub.3            5-OCH.sub. 3                                                                        H  H  CH                                         94   CH.sub.3            5-OCH.sub.3                                                                         H  H  N                                          95   CH.sub.3            6-OCH.sub.3                                                                         H  H  CH                                         96   CH.sub.3            6-OCH.sub.3                                                                         H  H  N                                          97   CH.sub.3CH.sub.2    H    H  H  CH oil (E)                                 98   CH.sub.3CH.sub.2    H    H  H  N  oil (E)                                 99   CH.sub.3CH.sub.2    2-Cl 5-Cl                                                                              H  CH                                        100   CH.sub.3CH.sub.2    2-Cl 5-Cl                                                                              H  N                                         101   CH.sub.3CH.sub.2    4-Cl H  H  CH                                        102   CH.sub.3CH.sub.2    4-Cl H  H  N                                         103   CH.sub.3CH.sub.2    4-CH.sub.3                                                                          H  H  CH                                        104   CH.sub.3CH.sub.2    4-CH.sub.3                                                                          H  H  N                                         105   CH.sub.3CH.sub.2    5-OCH.sub.3                                                                         H  H  CH                                        106   CH.sub.3CH.sub.2    5-OCH.sub.3                                                                         H  H  N                                         107   CH.sub.3CH.sub.2    6-OCH.sub.3                                                                         H  H  CH  96-98 (E)                             108   CH.sub.3CH.sub.2    6-OCH.sub.3                                                                         H  H  N  124-126 (E)                            109   CH.sub.3CH.sub.2CH.sub.2                                                                           H    H  H  CH                                        110   CH.sub.3CH.sub.2CH.sub.2                                                                           H    H  H  N                                         111   CH.sub. 2CHCH.sub.2 H    H  H  CH oil (E)                                112   CH.sub.2CHCH.sub.2  H    H  H  N  oil (E)                                113   CH.sub.3CH(CH.sub.3)                                                                               H    H  H  CH oil (E)                                114   CH.sub.3CH(CH.sub.3)                                                                               H    H  H  N  oil (E)                                115   HCCCH.sub.2         H    H  H  CH                                        116   HCCCH.sub.2         H    H  H  N                                         117   cyclo-C.sub.3 H.sub.5CH.sub.2                                                                      H    H  H  CH                                        118   cyclo-C.sub.3 H.sub.5CH.sub.2                                                                      H    H  H  N                                         119   CH.sub.3CH.sub.2CH.sub.2CH.sub.2                                                                   H    H  H  CH oil (E)                                120   CH.sub.3CH.sub.2CH.sub.2CH.sub.2                                                                   H    H  H  N  oil (E)                                121   CH.sub.3CHCHCH.sub.2                                                                               H    H  H  CH                                        122   CH.sub.3CHCHCH.sub.2                                                                               H    H  H  N                                         123   CH.sub.3(CH.sub.2).sub.5                                                                           H    H  H  CH oil (E)                                124   CH.sub.3(CH.sub.2).sub.5                                                                           H    H  H  N  oil (E)                                125   cyclo-C.sub.6 H.sub. 11                                                                            H    H  H  CH                                        126   cyclo-C.sub.6 H.sub.11                                                                             H    H  H  N                                         127   C.sub.6 H.sub.5CH.sub.2                                                                            H    H  H  CH oil (E)                                128   C.sub.6 H.sub.5CH.sub.2                                                                            H    H  H  N  oil (E)                                129   4-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H  H  CH                                        130   4-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H  H  N                                         131   3-CF.sub.3C.sub.6 H.sub.4CH.sub.2                                                                  H    H  H  CH                                        132   3-CF.sub.3C.sub.6 H.sub.4CH.sub.2                                                                  H    H  H  N                                         133   4-ClC.sub.6 H.sub.4CH.sub.2CH.sub.2                                                                H    H  H  CH                                        134   4-ClC.sub.6 H.sub.4CH.sub.2CH.sub.2                                                                H    H  H  N                                         135   C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2                                                            H    H  H  CH                                        136   C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2                                                            H    H  H  N                                         137   C.sub.6 H.sub.5(CH.sub.2).sub.4                                                                    H    H  H  CH                                        138   C.sub.6 H.sub.5(CH.sub.2).sub.4                                                                    H    H  H  N                                         139   C.sub.6 H.sub.5CH.sub.2CHCHCH.sub.2                                                                H    H  H  CH                                        140   C.sub.6 H.sub.5CH.sub.2CHCHCH.sub.2                                                                H    H  H  N                                         141   4-FC.sub.6 H.sub.4CHCHCH.sub.2CH.sub.2                                                             H    H  H  CH                                        142   4-FC.sub.6 H.sub.4CHCHCH.sub.2CH.sub.2                                                             H    H  H  N                                         143   t-C.sub.4 H.sub.9 OCOCH.sub.2                                                                      H    H  H  CH                                        144   t-C.sub.4 H.sub.9 OCOCH.sub.2                                                                      H    H  H  N                                         145   t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3                                                              H    H  H  CH                                        146   t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3                                                              H    H  H  N                                         147   ClCHCHCH.sub.2      H    H  H  CH                                        148   ClCHCHCH.sub.2      H    H  H  N                                         251   C.sub.2 H.sub.5     6-OC.sub.2 H.sub.5                                                                  H  H  CH  83-85 (E)                             252   C.sub.2 H.sub.5     6-OC.sub.2 H.sub.5                                                                  H  H  N  104-106 (E)                            253   CH.sub.3C(CH.sub.3).sub.2                                                                          H    H  H  CH                                        254   CH.sub.3C(CH.sub.3).sub.2                                                                          H    H  H  N                                         255   CH.sub.3CH(CH.sub.3)CH.sub.2                                                                       H    H  H  CH                                        256   CH.sub.3CH(CH.sub.3)CH.sub.2                                                                       H    H  H  N                                         257   CH.sub.2C(CH.sub.3)CH.sub.2                                                                        H    H  H  CH                                        258   CH.sub.2C(CH.sub.3)CH.sub.2                                                                        H    H  H  N                                         259   CH.sub.3CH(CH.sub.3)CH.sub.2CH.sub.2                                                               H    H  H  CH                                        260   CH.sub.3CH(CH.sub.3)CH.sub.2CH.sub.2                                                               H    H  H  N                                         261   CH.sub.3(CH.sub.2).sub.4                                                                           H    H  H  CH                                        262   CH.sub.3(CH.sub.2).sub.4                                                                           H    H  H  N  oil (E)                                263   2-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H  H  CH oil (E)                                264   2-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H  H  N  oil (E)                                265   3-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H  H  CH oil (E)                                266   3-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H  H  N  oil (E)                                267   2-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H  H  CH oil (E)                                268   2-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H  H  N                                         269   3,4-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H  H  CH oil (E)                                270   3,4-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H  H  N  oil (E)                                271   2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H  H  CH oil (E)                                272   2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H  H  N  oil (E)                                273   C.sub.6 H.sub.5CH.sub.2CH.sub.2                                                                    H    H  H  CH oil (E)                                274   C.sub.6 H.sub.5CH.sub.2CH.sub.2                                                                    H    H  H  N  oil (E)                                275   C.sub.6 H.sub.5CHCHCH.sub.2CH.sub.2                                                                H    H  H  CH oil (E)                                276   C.sub.6 H.sub.5CHCHCH.sub.2CH.sub.2                                                                H    H  H  N  oil (E)                                277   4-ClC.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                            H    H  H  CH oil (E)                                278   4-ClC.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                            H    H  H  N  oil (E)                                279   4-CF.sub.3C.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                      H    H  H  CH oil (E)                                280   4-CF.sub.3C.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                      H    H  H  N  oil (E)                                435   CH.sub.3            H    H  CH.sub.3                                                                          CH oil (E)                                436   CH.sub.3            H    H  CH.sub.3                                                                          N  oil (E)                                437   CH.sub.3            2-Cl 5-Cl                                                                              CH.sub.3                                                                          CH                                        438   CH.sub.3            2-Cl 5-Cl                                                                              CH.sub.3                                                                          N                                         439   CH.sub.3            4-Cl H  CH.sub.3                                                                          CH                                        440   CH.sub.3            4-Cl H  CH.sub.3                                                                          N                                         441   CH.sub.3            4-CH.sub.3                                                                          H  CH.sub.3                                                                          CH                                        442   CH.sub.3            4-CH.sub.3                                                                          H  CH.sub.3                                                                          N                                         443   CH.sub.3            5-OCH.sub.3                                                                         H  CH.sub.3                                                                          CH                                        444   CH.sub.3            5-OCH.sub.3                                                                         H  CH.sub.3                                                                          N                                         445   CH.sub.3            6-OCH.sub.3                                                                         H  CH.sub.3                                                                          CH                                        446   CH.sub.3            6-OCH.sub.3                                                                         H  CH.sub.3                                                                          N                                         447   CH.sub.3CH.sub.2    H    H  CH.sub.3                                                                          CH oil (E)                                448   CH.sub.3CH.sub.2    H    H  CH.sub.3                                                                          N  oil (E)                                449   CH.sub.3CH.sub.2    2-Cl 5-Cl                                                                              CH.sub.3                                                                          CH                                        450   CH.sub.3CH.sub.2    2-Cl 5-Cl                                                                              CH.sub.3                                                                          N                                         451   CH.sub.3CH.sub.2    4-Cl H  CH.sub.3                                                                          CH                                        452   CH.sub.3CH.sub.2    4-Cl H  CH.sub.3                                                                          N                                         453   CH.sub.3CH.sub.2    4-CH.sub.3                                                                          H  CH.sub.3                                                                          CH                                        454   CH.sub.3CH.sub.2    4-CH.sub.3                                                                          H  CH.sub.3                                                                          N                                         455   CH.sub.3CH.sub.2    5-OCH.sub.3                                                                         H  CH.sub.3                                                                          CH                                        456   CH.sub.3CH.sub.2    5-OCH.sub.3                                                                         H  CH.sub.3                                                                          N                                         457   CH.sub.3CH.sub.2    6-OCH.sub.3                                                                         H  CH.sub.3                                                                          CH                                        458   CH.sub.3CH.sub.2    6-OCH.sub.3                                                                         H  CH.sub.3                                                                          N                                         459   CH.sub.3CH.sub.2CH.sub.2                                                                           H    H  CH.sub.3                                                                          CH oil (E)                                460   CH.sub.3CH.sub.2CH.sub.2                                                                           H    H  CH.sub.3                                                                          N   73-74 (E)                             461   CH.sub.2CHCH.sub.2  H    H  CH.sub.3                                                                          CH oil (E)                                462   CH.sub.2CHCH.sub.2  H    H  CH.sub.3                                                                          N   51-53 (E)                             463   CH.sub.3CH(CH.sub.3)                                                                               H    H  CH.sub.3                                                                          CH oil (E)                                464   CH.sub.3CH(CH.sub.3)                                                                               H    H  CH.sub.3                                                                          N   58-60 (E)                             465   HCCCH.sub.2         H    H  CH.sub.3                                                                          CH                                        466   HCCCH.sub.2         H    H  CH.sub.3                                                                          N                                         467   cyclo-C.sub.3 H.sub.5CH.sub.2                                                                      H    H  CH.sub.3                                                                          CH                                        468   cyclo-C.sub.3 H.sub.5CH.sub.2                                                                      H    H  CH.sub.3                                                                          N                                         469   CH.sub.3CH.sub.2CH.sub.2CH.sub.2                                                                   H    H  CH.sub.3                                                                          CH oil (E)                                470   CH.sub.3CH.sub. 2CH.sub.2CH.sub.2                                                                  H    H  CH.sub.3                                                                          N  oil (E)                                471   CH.sub.3CHCHCH.sub.2                                                                               H    H  CH.sub.3                                                                          CH oil (E)                                472   CH.sub.3CHCHCH.sub.2                                                                               H    H  CH.sub.3                                                                          N   76-78 (E)                             473   CH.sub.3(CH.sub.2).sub.5                                                                           H    H  CH.sub.3                                                                          CH oil (E)                                474   CH.sub.3(CH.sub.2).sub.5                                                                           H    H  CH.sub.3                                                                          N  oil (E)                                475   cyclo-C.sub.6 H.sub.11                                                                             H    H  CH.sub.3                                                                          CH                                        476   cyclo-C.sub.6 H.sub.11                                                                             H    H  CH.sub.3                                                                          N                                         477   C.sub.6 H.sub.5CH.sub.2                                                                            H    H  CH.sub.3                                                                          CH                                        478   C.sub.6 H.sub.5CH.sub.2                                                                            H    H  CH.sub.3                                                                          N  oil (E)                                479   4-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H  CH.sub.3                                                                          CH                                        480   4-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H  CH.sub.3                                                                          N                                         481   3-CF.sub.3C.sub.6 H.sub.4CH.sub.2                                                                  H    H  CH.sub.3                                                                          CH                                        482   3-CF.sub.3C.sub.6 H.sub.4CH.sub.2                                                                  H    H  CH.sub.3                                                                          N                                         483   4-ClC.sub.6 H.sub.4CH.sub.2CH.sub.2                                                                H    H  CH.sub.3                                                                          CH                                        484   4-ClC.sub.6 H.sub.4CH.sub.2CH.sub.2                                                                H    H  CH.sub.3                                                                          N                                         485   C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2                                                            H    H  CH.sub.3                                                                          CH                                        486   C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2                                                            H    H  CH.sub.3                                                                          N                                         487   C.sub.6 H.sub.5(CH.sub.2).sub.4                                                                    H    H  CH.sub.3                                                                          CH                                        488   C.sub.6 H.sub.5(CH.sub.2).sub.4                                                                    H    H  CH.sub.3                                                                          N                                         489   C.sub.6 H.sub.5CH.sub.2CHCHCH.sub.2                                                                H    H  CH.sub.3                                                                          CH                                        490   C.sub.6 H.sub.5CH.sub.2CHCHCH.sub.2                                                                H    H  CH.sub.3                                                                          N                                         491   4-FC.sub.6 H.sub.4CHCHCH.sub.2CH.sub.2                                                             H    H  CH.sub.3                                                                          CH                                        492   4-FC.sub.6 H.sub.4CHCHCH.sub.2CH.sub.2                                                             H    H  CH.sub.3                                                                          N                                         493   t-C.sub.4 H.sub.9 OCOCH.sub.2                                                                      H    H  CH.sub.3                                                                          CH                                        494   t-C.sub.4 H.sub.9 OCOCH.sub.2                                                                      H    H  CH.sub.3                                                                          N                                         495   t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3                                                              H    H  CH.sub.3                                                                          CH                                        496   t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3                                                              H    H  CH.sub.3                                                                          N                                         497   ClCHCHCH.sub.2      H    H  CH.sub.3                                                                          CH oil (E)                                498   ClCHCHCH.sub.2      H    H  CH.sub.3                                                                          N  oil (E)                                499   C.sub.2 H.sub.5     6-OC.sub.2 H.sub.5                                                                  H  CH.sub.3                                                                          CH                                        500   C.sub.2 H.sub.5     6-OC.sub.2 H.sub.5                                                                  H  CH.sub.3                                                                          N                                         501   CH.sub.3C(CH.sub.3).sub.2                                                                          H    H  CH.sub.3                                                                          CH oil (E)                                502   CH.sub.3C(CH.sub.3).sub.2                                                                          H    H  CH.sub.3                                                                          N   83-85 (E)                             503   CH.sub.3CH(CH.sub.3)CH.sub.2                                                                       H    H  CH.sub.3                                                                          CH oil (E)                                504   CH.sub.3CH(CH.sub.3)CH.sub.2                                                                       H    H  CH.sub.3                                                                          N   70-72 (E)                             505   CH.sub.2C(CH.sub.3)CH.sub.2                                                                        H    H  CH.sub.3                                                                          CH oil (E)                                506   CH.sub.2C(CH.sub.3)CH.sub.2                                                                        H    H  CH.sub.3                                                                          N   64-65 (E)                             507   CH.sub.3CH(CH.sub.3)CH.sub.2CH.sub.2                                                               H    H  CH.sub.3                                                                          CH oil (E)                                508   CH.sub.3CH(CH.sub.3)CH.sub.2CH.sub.2                                                               H    H  CH.sub.3                                                                          N  oil (E)                                509   CH.sub.3(CH.sub.2).sub.4                                                                           H    H  CH.sub.3                                                                          CH                                        510   CH.sub.3(CH.sub.2).sub.4                                                                           H    H  CH.sub.3                                                                          N                                         511   2-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H  CH.sub.3                                                                          CH                                        512   2-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H  CH.sub.3                                                                          N                                         513   3-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H  CH.sub.3                                                                          CH                                        514   3-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H  CH.sub.3                                                                          N                                         515   2-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H  CH.sub.3                                                                          CH                                        516   2-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H  CH.sub.3                                                                          N                                         517   3,4-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H  CH.sub.3                                                                          CH                                        518   3,4-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H  CH.sub.3                                                                          N                                         519   2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H  CH.sub.3                                                                          CH                                        520   2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H  CH.sub.3                                                                          N                                         521   C.sub.6 H.sub.5CH.sub.2CH.sub.2                                                                    H    H  CH.sub.3                                                                          CH                                        522   C.sub.6 H.sub.5CH.sub.2CH.sub.2                                                                    H    H  CH.sub.3                                                                          N                                         523   C.sub.6 H.sub.5CHCHCH.sub.2CH.sub.2                                                                H    H  CH.sub.3                                                                          CH                                        524   C.sub.6 H.sub.5CHCHCH.sub.2CH.sub.2                                                                H    H  CH.sub.3                                                                          N                                         525   4-ClC.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                            H    H  CH.sub.3                                                                          CH                                        526   4-ClC.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                            H    H  CH.sub.3                                                                          N                                         527   4-CF.sub.3C.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                      H    H  CH.sub.3                                                                          CH                                        528   4-CF.sub.3C.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                      H    H  CH.sub.3                                                                          N                                         529   CH.sub.3            H    H  C.sub.6 H.sub.5                                                                   CH                                        530   CH.sub.3            H    H  C.sub.6 H.sub.5                                                                   N                                         531   C.sub.2 H.sub.5     H    H  C.sub.6 H.sub.5                                                                   CH                                        532   C.sub.2 H.sub.5     H    H  C.sub.6 H.sub.5                                                                   N                                         533   CH.sub.3CH.sub.2CH.sub.2                                                                           H    H  C.sub.6 H.sub.5                                                                   CH                                        534   CH.sub.3CH.sub.2CH.sub.2                                                                           H    H  C.sub.6 H.sub.5                                                                   N                                         535   CH.sub.3(CH.sub.2).sub.5                                                                           H    H  C.sub.6 H.sub.5                                                                   CH                                        536   CH.sub.3(CH.sub.2).sub.5                                                                           H    H  C.sub.6 H.sub.5                                                                   N                                         537   C.sub.6 H.sub.5CH.sub.2                                                                            H    H  C.sub.6 H.sub.5                                                                   CH                                        538   C.sub.6 H.sub.5CH.sub.2                                                                            H    H  C.sub.6 H.sub.5                                                                   N                                         __________________________________________________________________________

                                      TABLE 3                                      __________________________________________________________________________     Compounds of the formula Ic (4-position of the oxime ether).                   The configuration statement relates to the methyl                              β-methoxyacrylate group or the methyl glyoxylate O-methyloxime            group.                                                                          ##STR12##                                  Ic                                 Comp. no.                                                                            R.sup.1             R.sup.2                                                                             R.sup.3                                                                           R.sup.4                                                                           X  mp. (°C.)                       __________________________________________________________________________     149   CH.sub.3            H    H  H  CH  84-86 (E)                             150   CH.sub.3            H    H  H  N   88-91 (E)                             151   CH.sub.3            2-Cl H  H  CH                                        152   CH.sub.3            2-Cl H  H  N                                         153   CH.sub.3            2-CH.sub.3                                                                          H  H  CH                                        154   CH.sub.3            2-CH.sub.3                                                                          H  H  N                                         155   CH.sub.3            2-OCH.sub.3                                                                         H  H  CH oil (E)                                156   CH.sub.3            2-OCH.sub.3                                                                         H  H  N  105-107 (E)                            157   CH.sub.3            3-Cl H  H  CH                                        158   CH.sub.3            3-Cl H  H  N                                         159   CH.sub.3            3-CH.sub.3                                                                          H  H  CH                                        160   CH.sub.3            3-CH.sub.3                                                                          H  H  N                                         161   CH.sub.3            3-OCH.sub.3                                                                         H  H  CH                                        162   CH.sub.3            3-OCH.sub.3                                                                         H  H  N                                         163   CH.sub.3            2-Cl 6-Cl                                                                              H  CH                                        164   CH.sub.3            2-Cl 6-Cl                                                                              H  N                                         165   CH.sub.3CH.sub.2    H    H  H  CH 108-110 (E)                            166   CH.sub.3CH.sub.2    H    H  H  N  106-108 (E)                            167   CH.sub.3CH.sub.2    2-Cl H  H  CH                                        168   CH.sub.3CH.sub.2    2-Cl H  H  N                                         169   CH.sub.3CH.sub.2    2-CH.sub.3                                                                          H  H  CH                                        170   CH.sub.3CH.sub.2    2-CH.sub.3                                                                          H  H  N                                         171   CH.sub.3CH.sub.2    2-OCH.sub.3                                                                         H  H  CH                                        172   CH.sub.3CH.sub.2    2-OCH.sub.3                                                                         H  H  N                                         173   CH.sub.3CH.sub.2    3-Cl H  H  CH                                        174   CH.sub.3CH.sub.2    3-Cl H  H  N                                         175   CH.sub.3CH.sub.2    3-CH.sub.3                                                                          H  H  CH                                        176   CH.sub.3CH.sub.2    3-CH.sub.3                                                                          H  H  N                                         177   CH.sub.3CH.sub.2    3-OCH.sub.3                                                                         H  H  CH                                        178   CH.sub.3CH.sub.2    3-OCH.sub.3                                                                         H  H  N                                         179   CH.sub.3CH.sub.2    2-Cl 6-Cl                                                                              H  CH                                        180   CH.sub.3CH.sub.2    2-Cl 6-Cl                                                                              H  N                                         181   CH.sub.3CH.sub.2CH.sub.2                                                                           H    H  H  CH                                        182   CH.sub.3CH.sub.2CH.sub.2                                                                           H    H  H  N                                         183   CH.sub.2CHCH.sub.2  H    H  H  CH 103-105 (E)                            184   CH.sub.2CHCH.sub.2  H    H  H  N   82-84 (E)                             185   CH.sub.3CH(CH.sub.3)                                                                               H    H  H  CH                                        186   CH.sub.3CH(CH.sub.3)                                                                               H    H  H  N                                         187   HCCCH.sub.2         H    H  H  CH                                        188   HCCCH.sub.2         H    H  H  N                                         189   cyclo-C.sub.3 H.sub.5CH.sub.2                                                                      H    H  H  CH                                        190   cyclo-C.sub.3 H.sub.5CH.sub.2                                                                      H    H  H  N                                         191   CH.sub.3CH.sub.2CH.sub.2CH.sub.2                                                                   H    H  H  CH                                        192   CH.sub.3CH.sub.2CH.sub.2CH.sub.2                                                                   H    H  H  N                                         193   CH.sub.3 CHCHCH.sub.2                                                                              H    H  H  CH                                        194   CH.sub.3CHCHCH.sub.2                                                                               H    H  H  N                                         195   CH.sub.3(CH.sub.2).sub.5                                                                           H    H  H  CH  62-63 (E)                             196   CH.sub.3(CH.sub.2).sub.5                                                                           H    H  H  N   72-73 (E)                             197   cyclo-C.sub.6 H.sub.11                                                                             H    H  H  CH                                        198   cyclo-C.sub.6 H.sub.11                                                                             H    H  H  N                                         199   C.sub.6 H.sub.5CH.sub.2                                                                            H    H  H  CH 103-105 (E)                            200   C.sub.6 H.sub.5CH.sub.2                                                                            H    H  H  N  151-153 (E)                            201   4-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H  H  CH                                        202   4-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H  H  N                                         203   3-CF.sub.3C.sub.6 H.sub.4CH.sub.2                                                                  H    H  H  CH                                        204   3-CF.sub.3C.sub.6 H.sub.4CH.sub.2                                                                  H    H  H  N                                         205   4-ClC.sub.6 H.sub.4CH.sub.2CH.sub.2                                                                H    H  H  CH                                        206   4-ClC.sub.6 H.sub.4CH.sub.2CH.sub.2                                                                H    H  H  N                                         207   C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2                                                            H    H  H  CH                                        208   C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2                                                            H    H  H  N                                         209   C.sub.6 H.sub.5(CH.sub.2).sub.4                                                                    H    H  H  CH                                        210   C.sub.6 H.sub.5(CH.sub.2).sub.4                                                                    H    H  H  N                                         211   C.sub.6 H.sub.5CH.sub.2CHCHCH.sub.2                                                                H    H  H  CH                                        212   C.sub.6 H.sub.5CH.sub.2CHCHCH.sub.2                                                                H    H  H  N                                         213   4-FC.sub.6 H.sub.4CHCHCH.sub.2CH.sub.2                                                             H    H  H  CH                                        214   4-FC.sub.6 H.sub.4CHCHCH.sub.2CH.sub.2                                                             H    H  H  N                                         215   t-C.sub.4 H.sub.9 OCOCH.sub.2                                                                      H    H  H  CH                                        216   t-C.sub.4 H.sub.9 OCOCH.sub.2                                                                      H    H  H  N                                         217   t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3                                                              H    H  H  CH                                        218   t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3                                                              H    H  H  N                                         219   ClCHCHCH.sub.2      H    H  H  CH oil (E)                                220   ClCHCHCH.sub.2      H    H  H  N   95-97 (E)                             281   C.sub.2 H.sub.5     6-OC.sub.2 H.sub.5                                                                  H  H  CH                                        282   C.sub.2 H.sub.5     6-OC.sub.2 H.sub.5                                                                  H  H  N                                         283   CH.sub.3C(CH.sub.3).sub.2                                                                          H    H  H  CH                                        284   CH.sub.3C(CH.sub.3).sub.2                                                                          H    H  H  N                                         285   CH.sub.3CH(CH.sub.3)CH.sub.2                                                                       H    H  H  CH                                        286   CH.sub.3CH(CH.sub.3)CH.sub.2                                                                       H    H  H  N                                         287   CH.sub.2C(CH.sub.3)CH.sub.2                                                                        H    H  H  CH 100-102 (E)                            288   CH.sub.2C(CH.sub.3)CH.sub.2                                                                        H    H  H  N   95-96 (E)                             289   CH.sub.3CH(CH.sub.3)CH.sub.2CH.sub.2                                                               H    H  H  CH                                        290   CH.sub.3CH(CH.sub.3)CH.sub.2CH.sub.2                                                               H    H  H  N                                         291   CH.sub.3(CH.sub.2).sub.4                                                                           H    H  H  CH                                        292   CH.sub.3(CH.sub.2).sub.4                                                                           H    H  H  N  oil (E)                                293   2-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H  H  CH                                        294   2-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H  H  N                                         295   3-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H  H  CH                                        296   3-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H  H  N                                         297   2-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H  H  CH                                        298   2-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H  H  N                                         299   3,4-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H  H  CH                                        300   3,4-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H  H  N                                         301   2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H  H  CH                                        302   2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H  H  N                                         303   C.sub.6 H.sub.5CH.sub.2CH.sub.2                                                                    H    H  H  CH                                        304   C.sub.6 H.sub.5CH.sub.2CH.sub.2                                                                    H    H  H  N                                         305   C.sub.6 H.sub.5CHCHCH.sub.2CH.sub.2                                                                H    H  H  CH                                        306   C.sub.6 H.sub.5CHCHCH.sub.2CH.sub.2                                                                H    H  H  N                                         307   4-ClC.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                            H    H  H  CH                                        308   4-ClC.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                            H    H  H  N                                         309   4-CF.sub.3C.sub.6 H.sub.4CH.sub.2CH CHCH.sub.2                                                     H    H  H  CH                                        310   4-CF.sub.3C.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                      H    H  H  N                                         539   CH.sub.3            H    H  CH.sub.3                                                                          CH oil (E)                                540   CH.sub.3            H    H  CH.sub.3                                                                          N   99-100 (E)                            541   CH.sub.3            2-Cl H  CH.sub.3                                                                          CH                                        542   CH.sub.3            2-Cl H  CH.sub.3                                                                          N                                         543   CH.sub.3            2-CH.sub.3                                                                          H  CH.sub.3                                                                          CH                                        544   CH.sub.3            2-CH.sub.3                                                                          H  CH.sub.3                                                                          N                                         545   CH.sub.3            2-OCH.sub.3                                                                         H  CH.sub.3                                                                          CH                                        546   CH.sub.3            2-OCH.sub.3                                                                         H  CH.sub.3                                                                          N                                         547   CH.sub.3            3-Cl H  CH.sub.3                                                                          CH                                        548   CH.sub.3            3-Cl H  CH.sub.3                                                                          N                                         549   CH.sub.3            3-CH.sub.3                                                                          H  CH.sub.3                                                                          CH                                        550   CH.sub.3            3-CH.sub.3                                                                          H  CH.sub.3                                                                          N                                         551   CH.sub.3            3-OCH.sub.3                                                                         H  CH.sub.3                                                                          CH                                        552   CH.sub.3            3-OCH.sub.3                                                                         H  CH.sub.3                                                                          N                                         553   CH.sub.3            2-Cl 6-Cl                                                                              CH.sub.3                                                                          CH                                        554   CH.sub.3            2-Cl 6-Cl                                                                              CH.sub.3                                                                          N                                         555   CH.sub.3CH.sub.2    H    H  CH.sub.3                                                                          CH  71-73 (E)                             556   CH.sub.3CH.sub.2    H    H  CH.sub.3                                                                          N   79-80 (E)                             557   CH.sub.3CH.sub. 2   2-Cl H  CH.sub.3                                                                          CH                                        558   CH.sub.3CH.sub.2    2-Cl H  CH.sub.3                                                                          N                                         559   CH.sub.3CH.sub.2    2-CH.sub.3                                                                          H  CH.sub.3                                                                          CH                                        560   CH.sub.3CH.sub.2    2-CH.sub.3                                                                          H  CH.sub.3                                                                          N                                         561   CH.sub.3CH.sub.2    2-OCH.sub.3                                                                         H  CH.sub.3                                                                          CH                                        562   CH.sub.3CH.sub.2    2-OCH.sub.3                                                                         H  CH.sub.3                                                                          N                                         563   CH.sub.3CH.sub.2    3-Cl H  CH.sub.3                                                                          CH                                        564   CH.sub.3CH.sub.2    3-Cl H  CH.sub.3                                                                          N                                         565   CH.sub.3CH.sub.2    3-CH.sub.3                                                                          H  CH.sub.3                                                                          CH                                        566   CH.sub.3CH.sub.2    3-CH.sub.3                                                                          H  CH.sub.3                                                                          N                                         567   CH.sub.3CH.sub.2    3-OCH.sub.3                                                                         H  CH.sub.3                                                                          CH                                        568   CH.sub.3CH.sub.2    3-OCH.sub.3                                                                         H  CH.sub.3                                                                          N                                         569   CH.sub.3CH.sub.2    2-Cl 6-Cl                                                                              CH.sub.3                                                                          CH                                        570   CH.sub.3CH.sub.2    2-Cl 6-Cl                                                                              CH.sub.3                                                                          N                                         571   CH.sub.3CH.sub.2CH.sub.2                                                                           H    H  CH.sub.3                                                                          CH  97-99 (E)                             572   CH.sub.3CH.sub.2CH.sub.2                                                                           H    H  CH.sub.3                                                                          N  100-101 (E)                            573   CH.sub.2CHCH.sub.2  H    H  CH.sub.3                                                                          CH  90-92 (E)                             574   CH.sub.2CHCH.sub.2  H    H  CH.sub.3                                                                          N  107-108 (E)                            575   CH.sub.3CH(CH.sub.3)                                                                               H    H  CH.sub.3                                                                          CH 120-123 (E)                            576   CH.sub.3CH(CH.sub.3)                                                                               H    H  CH.sub.3                                                                          N  109-110 (E)                            577   HCCCH.sub.2         H    H  CH.sub.3                                                                          CH                                        578   HCCCH.sub.2         H    H  CH.sub.3                                                                          N                                         579   cyclo-C.sub.3 H.sub.5CH.sub.2                                                                      H    H  CH.sub.3                                                                          CH                                        580   cyclo-C.sub.3 H.sub.5CH.sub.2                                                                      H    H  CH.sub.3                                                                          N                                         581   CH.sub.3CH.sub.2CH.sub.2CH.sub.2                                                                   H    H  CH.sub.3                                                                          CH  64-66 (E)                             582   CH.sub.3CH.sub.2CH.sub.2CH.sub.2                                                                   H    H  CH.sub.3                                                                          N  oil (E)                                583   CH.sub.3CHCHCH.sub.2                                                                               H    H  CH.sub.3                                                                          CH oil (E)                                584   CH.sub.3CHCHCH.sub.2                                                                               H    H  CH.sub.3                                                                          N  100-103 (E)                            585   CH.sub.3(CH.sub.2).sub.5                                                                           H    H  CH.sub.3                                                                          CH  65-67 (E)                             586   CH.sub.3(CH.sub.2).sub.5                                                                           H    H  CH.sub.3                                                                          N   60-63 (E)                             587   cyclo-C.sub.6 H.sub.11                                                                             H    H  CH.sub.3                                                                          CH                                        588   cyclo-C.sub.6 H.sub.11                                                                             H    H  CH.sub.3                                                                          N                                         589   C.sub.6 H.sub.5CH.sub.2                                                                            H    H  CH.sub.3                                                                          CH 110-112 (E)                            590   C.sub.6 H.sub.5CH.sub.2                                                                            H    H  CH.sub.3                                                                          N  104-106 (E)                            591   4-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H  CH.sub.3                                                                          CH                                        592   4-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H  CH.sub.3                                                                          N                                         593   3-CF.sub.3C.sub.6 H.sub.4CH.sub.2                                                                  H    H  CH.sub.3                                                                          CH                                        594   3-CF.sub.3C.sub.6 H.sub.4CH.sub.2                                                                  H    H  CH.sub.3                                                                          N                                         595   4-ClC.sub.6 H.sub.4CH.sub.2CH.sub.2                                                                H    H  CH.sub.3                                                                          CH                                        596   4-ClC.sub.6 H.sub.4CH.sub.2CH.sub.2                                                                H    H  CH.sub.3                                                                          N                                         597   C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2                                                            H    H  CH.sub.3                                                                          CH                                        598   C.sub.6 H.sub.5CH.sub.2CH.sub.2CH.sub.2                                                            H    H  CH.sub.3                                                                          N                                         599   C.sub.6 H.sub.5(CH.sub.2).sub.4                                                                    H    H  CH.sub.3                                                                          CH                                        600   C.sub.6 H.sub.5(CH.sub.2).sub.4                                                                    H    H  CH.sub.3                                                                          N                                         601   C.sub.6 H.sub.5CH.sub.2CHCHCH.sub.2                                                                H    H  CH.sub.3                                                                          CH                                        602   C.sub.6 H.sub.5CH.sub.2CHCHCH.sub.2                                                                H    H  CH.sub.3                                                                          N                                         603   4-FC.sub. 6 H.sub.4CHCHCH.sub.2CH.sub.2                                                            H    H  CH.sub.3                                                                          CH                                        604   4-FC.sub.6 H.sub.4CHCHCH.sub.2CH.sub.2                                                             H    H  CH.sub.3                                                                          N                                         605   t-C.sub.4 H.sub.9 OCOCH.sub.2                                                                      H    H  CH.sub.3                                                                          CH                                        606   t-C.sub.4 H.sub.9 OCOCH.sub.2                                                                      H    H  CH.sub.3                                                                          N                                         607   t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3                                                              H    H  CH.sub.3                                                                          CH                                        608   t-C.sub.4 H.sub.9 OCO(CH.sub.2).sub.3                                                              H    H  CH.sub.3                                                                          N                                         609   ClCHCHCH.sub.2      H    H  CH.sub.3                                                                          CH  98-100 (E)                            610   ClCHCHCH.sub.2      H    H  CH.sub.3                                                                          N  105-107 (E)                            611   C.sub.2 H.sub.5     6-OC.sub.2 H.sub.5                                                                  H  CH.sub.3                                                                          CH                                        612   C.sub.2 H.sub.5     6-OC.sub.2 H.sub.5                                                                  H  CH.sub.3                                                                          N                                         613   CH.sub.3C(CH.sub.3).sub.2                                                                          H    H  CH.sub.3                                                                          CH  88-90 (E)                             614   CH.sub.3C(CH.sub.3).sub.2                                                                          H    H  CH.sub.3                                                                          N   75-78 (E)                             615   CH.sub.3CH(CH.sub.3)CH.sub.2                                                                       H    H  CH.sub.3                                                                          CH  85-87 (E)                             616   CH.sub.3CH(CH.sub.3 )CH.sub.2                                                                      H    H  CH.sub.3                                                                          N   79-81 (E)                             617   CH.sub.2C(CH.sub.3)CH.sub.2                                                                        H    H  CH.sub.3                                                                          CH  94-96 (E)                             618   CH.sub.2C(CH.sub.3)CH.sub.2                                                                        H    H  CH.sub.3                                                                          N   88-89 (E)                             619   CH.sub.3CH(CH.sub.3)CH.sub.2CH.sub.2                                                               H    H  CH.sub.3                                                                          CH  46-48 (E)                             620   CH.sub.3CH(CH.sub.3)CH.sub.2CH.sub.2                                                               H    H  CH.sub.3                                                                          N  oil (E)                                621   CH.sub.3(CH.sub.2).sub.4                                                                           H    H  CH.sub.3                                                                          CH                                        622   CH.sub.3(CH.sub.2).sub.4                                                                           H    H  CH.sub.3                                                                          N                                         623   2-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H  CH.sub.3                                                                          CH                                        624   2-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H  CH.sub.3                                                                          N                                         625   3-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H  CH.sub.3                                                                          CH                                        626   3-FC.sub.6 H.sub.4CH.sub.2                                                                         H    H  CH.sub.3                                                                          N                                         627   2-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H  CH.sub.3                                                                          CH                                        628   2-ClC.sub.6 H.sub.4CH.sub.2                                                                        H    H  CH.sub.3                                                                          N                                         629   3,4-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H  CH.sub.3                                                                          CH                                        630   3,4-Cl.sub. 2C.sub.6 H.sub.3CH.sub.2                                                               H    H  CH.sub.3                                                                          N                                         631   2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H  CH.sub.3                                                                          CH                                        632   2,6-Cl.sub.2C.sub.6 H.sub.3CH.sub.2                                                                H    H  CH.sub.3                                                                          N                                         633   C.sub.6 H.sub.5CH.sub.2CH.sub.2                                                                    H    H  CH.sub.3                                                                          CH                                        634   C.sub.6 H.sub.5CH.sub.2CH.sub.2                                                                    H    H  CH.sub.3                                                                          N                                         635   C.sub.6 H.sub.5CHCHCH.sub.2CH.sub.2                                                                H    H  CH.sub.3                                                                          CH                                        636   C.sub.6 H.sub.5CHCHCH.sub.2CH.sub.2                                                                H    H  CH.sub.3                                                                          N                                         637   4-ClC.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                            H    H  CH.sub.3                                                                          CH                                        638   4-ClC.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                            H    H  CH.sub.3                                                                          N                                         639   4-CF.sub.3C.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                      H    H  CH.sub.3                                                                          CH                                        640   4-CF.sub.3C.sub.6 H.sub.4CH.sub.2CHCHCH.sub.2                                                      H    H  CH.sub.3                                                                          N                                         641   CH.sub.3            H    H  C.sub.6 H.sub.5                                                                   CH                                        642   CH.sub.3            H    H  C.sub.6 H.sub.5                                                                   N                                         643   C.sub.2 H.sub.5     H    H  C.sub.6 H.sub. 5                                                                  CH                                        644   C.sub.2 H.sub.5     H    H  C.sub.6 H.sub.5                                                                   N                                         645   CH.sub.3CH.sub.2CH.sub.2                                                                           H    H  C.sub.6 H.sub.5                                                                   CH                                        646   CH.sub.3CH.sub.2CH.sub.2                                                                           H    H  C.sub.6 H.sub.5                                                                   N                                         647   CH.sub.3(CH.sub.2).sub.5                                                                           H    H  C.sub.6 H.sub.5                                                                   CH                                        648   CH.sub.3(CH.sub.2).sub.5                                                                           H    H  C.sub.6 H.sub.5                                                                   N                                         649   C.sub.6 H.sub.5CH.sub.2                                                                            H    H  C.sub.6 H.sub.5                                                                   CH                                        650   C.sub.6 H.sub.5CH.sub.2                                                                            H    H  C.sub.6 H.sub.5                                                                   N                                         __________________________________________________________________________

Table 4

¹ H-NMR data of selected compounds from Tables 1, 2 and 3. The chemical shift (δ) is given in ppm relative to tetramethylsilane. The solvent employed is CDCl₃.

Compound no. 1

3.67 (s, 3H); 3.77 (s, 3H); 3.93 (s, 3H); 4.98 (s, 2H); 6.81-7.81 (m, 8H); 7.57 (s, 1H); 8.49 (s, 1H).

Compound no. 2

3.40 (s, 3H); 3.95 (s, 3H); 4.05 (s, 3H); 4.95 (s, 2H); 6.80-7.85 (m, 8H); 8.45 (s, 1H).

Compound no. 23

1.31 (t, 3H); 3.67 (s, 3H); 3.79 (s, 3H); 4.20 (q, 2H); 4.97 (s, 2H); 6.83-7.83 (m, 8H); 7.59 (s, 1H); 8.51 (s, 1H).

Compound no. 24

1.30 (t, 3H); 3.80 (s, 3H); 4.05 (s, 3H); 4.20 (q, 2H); 4.95 (s, 2H); 6.80-7.85 (m, 8H); 8.45 (s, 1H).

Compound no. 85

3.65 (s, 3H); 3.68 (s, 3H); 3.92 (s, 3H); 4.95 (s, 2H); 6.85-7.52 (m, 8H); 7.55 (s, 1H); 7.98 (s, 1H).

Compound no. 97

1.28 (t, 3H); 3.68 (s, 3H); 3.73 (s, 3H); 4.20 (q, 2H); 4.97 (s, 2H); 6.85-7.53 (m, 8H); 7.57 (s, 1H); 8.00 (s, 1H).

Compound no. 149

3.68 (s, 3H); 3.77 (s, 3H); 3.92 (s, 3H); 4.98 (s, 2H); 6.87-7.53 (m, 8H); 7.59 (s, 1H); 7.98 (s, 1H).

Compound no. 165

1.31 (t, 3H); 3.69 (s, 3H); 3.80 (s, 3H); 4.20 (q, 2H); 5.00 (s, 2H); 6.87-7.53 (m, 8H); 7.60 (s, 1H); 8.00 (s, 1H).

Compound no. 447

1.32 (t, 3H); 2.18 (s, 3H); 3.68 (s, 3H); 3.77 (s, 3H); 4.22 (q, 2H); 4.97 (s, 2H); 6.83-7.53 (m, 8H); 7.55 (s, 1H).

Compound no. 488

1.32 (t, 3H); 2.17 (s, 3H); 3.82 (s, 3H); 4.00 (s, 3H); 4.23 (q, 4H); 4.97 (s, 2H); 6.83-7.57 (m, 8H).

Compound no. 470

0.95 (t, 3H); 1.43 (m, 2H); 1.70 (m, 2H); 2.18 (s, 3H); 3.83 (s, 3H); 4.00 (s, 3H); 4.17 (t, 2H); 4.97 (s, 2H); 6.82-7.55 (m, 8).

Compound no. 474

0.87 (t, 3H); 1.32 (m, 6H); 1.70 (m, 2H); 2.18 (s, 3H); 3.83 (s, 3H); 4.02 (s, 3H); 4.17 (t, 2H); 4.95 (s, 2H); 6.83-7.57 (m, 8H).

Compound no. 478

2.22 (s, 3H); 3.78 (s, 3H); 4.00 (s, 3H); 4.97 (s, 2H); 5.23 (s, 2H); 6.82-7.53 (m, 8H).

Compound no. 556

1.33 (t, 3H); 2.20 (s, 3H); 3.83 (s, 3H); 4.02 (s, 3H); 4.22 (q, 2H); 4.97 (s, 2H); 6.85-7.60 (m, 8H).

Compound no. 582

0.97 (t, 3H); 1.40 (m, 2H); 1.68 (m, 2H); 2.17 (s, 3H); 3.83 (s, 3H); 4.00 (s, 3H); 4.15 (t, 2H); 4.95 (s, 2H); 6.82-7.57 (m, 8H).

Compound no. 586

0.88 (t, 3H); 1.32 (m, 6H); 1.70 (m, 2H); 2.18 (s, 3H); 3.83 (s, 3H); 4.01 (s, 3H); 4.15 (t, 2H); 4.95 (s, 2H); 6.83-7.57 (m, 8H).

Compound no. 590

2.22 (s, 3H); 3.83 (s, 3H); 4.02 (s, 3H); 4.95 (s, 2H); 5.22 (s, 2H); 6.82-7.57 (m, 8H).

Generally speaking, the novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the Ascomycetes and Basidiomycetes classes. Some of them have a systemic action and can be used as foliar and soil fungicides.

The fungicidal compounds are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in vegetables such as cucumbers, beans and cucurbits.

The novel compounds are particularly useful for controlling the following plant diseases:

Erysiphe graminis in cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

Podosphaera leucotricha in apples,

Uncinula necator in vines,

Puccinia species in cereals,

Rhizoctonia species in cotton and lawns,

Ustilago species in cereals and sugar cane,

Venturia inaequalis (scab) in apples,

Helminthosporium species in cereals,

Septoria nodorum in wheat,

Botrytis cinerea (gray mold) in strawberries and grapes,

Cercospora arachidicola in groundnuts,

Pseudocercosporella herpotrichoides in wheat and barley,

Pyricularia oryzae in rice,

Phytophthora infestans in potatoes and tomatoes,

Fusarium and Verticillium species in various plants,

Plasmopara viticola in grapes,

Alternaria species in fruit and vegetables.

The compounds are applied by spraying or dusting the plants with the active ingredients, or treating the seeds of the plants with the active ingredients. They may be applied before or after infection of the plants or seeds by the fungi.

The novel substances can be converted into conventional formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application forms depend entirely on the purposes for which they are intended; they should at all event ensure a fine and uniform distribution of the active ingredient. The formulations are produced in known manner, for example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifier and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics (e.g., xylene), chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g., crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), and water; carriers such as ground natural minerals (e.g., kaolins, aluminas, talc and chalk) and ground synthetic minerals (e.g., highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as lignin, sulfite waste liquors and methylcellulose.

The fungicidal agents generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt % of active ingredient. The application rates are from 0.02 to 3 kg or more of active ingredient per hectare, depending on the type of effect desired. The novel compounds may also be used for protecting materials, for example against Paecilomyces variotii.

The agents and the ready-to-use formulations prepared from them, such as solutions, emulsions, suspensions, powders, dusts, pastes and granules, are applied in conventional manner, for example by spraying, atomizing, dusting, scattering, dressing or watering.

Examples of formulations are given below.

I. 90 parts by weight of compound no. 85 is mixed with 10 parts by weight of N-methyl-α-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

II. 20 parts by weight of compound no. 97 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.

III. 20 parts by weight of compound no. 447 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and finely distributing it therein, an aqueous dispersion is obtained.

IV. 20 parts by weight of compound no. 470 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210° and 280° C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.

V. 80 parts by weight of compound no. 149 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained.

VI. 3 parts by weight of compound no. 165 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

VII. 30 parts by weight of compound no. 590 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

VIII. 40 parts by weight of compound no. 448 is intimately mixed with 10 parts by weight of the sodium salt of a phenosulfonic acid-urea-formaldehye condensate, 2 parts of silica gel and 48 parts of water to give a stable aqueous dispersion. Dilution in water gives an aqueous dispersion.

IX. 20 parts by weight of compound no. 85 is intimately mixed with 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenosulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.

In these application forms, the agents according to the invention may also be present together with other active ingredients, for example herbicides, insecticides, growth regulators, and fungicides, and may furthermore be mixed and applied together with fertilizers. Admixtue with other fungicides frequently results in an increase in the fungicidal spectrum.

USE EXAMPLES

The comparative agent which was employed was methyl 2-(phenoxymethyl)phenylglyoxylate O-methyloxime (A) disclosed in EP 253,213.

USE EXAMPLE 1 Action on wheat brown rust

Leaves of pot-grown wheat seedlings of the "Kanzler" variety were dusted with spores of brown rust (Puccinia recondita). The pots were then placed for 24 hours at 20° to 22° C. in a high-humidity (90-95%) chamber. During this period the spores germinated and the germ tubes penetrated the leaf tissue. The infected plants were then sprayed to runoff with aqueous liquors containing (dry basis) 80% of active ingredient and 20% of emulsifier. After the sprayed-on layer had dried, the plants were set up in the greenhouse at 20° to 22° C. and a relative humidity of 65 to 70%. The extent of rust fungus spread on the leaves was assessed after 8 days.

The results show that active ingredients 85 and 97, applied as 0.025 wt % spray liquors, have a better fungicidal action (100%) than prior art comparative agent A (35%).

In another experiment, it was found that active ingredients 111, 112, 113, 119, 123, 195, 220, 262, 265, 266, 273, 275, 447 and 470, applied as 0.025 wt % spray liquors, have a better fungicidal action (95%) than prior art comparative agent A (35%).

USE EXAMPLE 2 Action on Plasmopara viticola

Leaves of potted vines of the Muller-Thurgau variety were sprayed with aqueous liquors containing (dry basis) 80% of active ingredient and 20% of emulsifier. To assess the duration of action, the plants were set up, after the sprayed-on layer had dried, for 8 days in the greenhouse. Then the leaves were infected with a zoospore suspension of Plasmopara viticola. The plants were first placed for 48 hours in a water vapor-saturated chamber at 24° C. and then in a greenhouse for 5 days at from 20° to 30° C. To accelerate and intensify the sporangiophore discharge, the plants were then again placed in the moist chamber for 16 hours. The extent of fungus attack was then assessed on the undersides of the leaves.

The results show that active ingredients 85, 97, 149 and 165, applied as 0.0125% spray liquors, have a better fungicidal action (100%) than prior art comparative agent A (50%).

In a further experiment, it was found that active ingredients 86, 88, 111, 113, 114, 119, 120, 123, 124, 127, 150, 155, 183, 184, 199, 219, 220, 263, 265, 267, 273, 275, 277, 287, 288, 447 and 448, applied as 0.0125% spray liquors, have a better fungicidal action (95%) than prior art comparative agent A (50%). 

We claim:
 1. A substituted oxime ether of the general formula I ##STR13## where R¹ is C₁ -C₆ -alkyl, C₃ -C₆ -alkenyl, C₃ -C₄ -alkynyl, C₁ -C₆ -haloalkyl, C₃ -C₆ -haloalkenyl, C₁ -C₄ -alkoxy-C₁ -C₆ -alkyl, C₃ -C₆ -cycloalkyl, C₃ -C₆ -cycloalkyl-C₁ -C₄ -alkyl, cyano-C₁ -C₆ -alkyl, C₁ -C₆ -alkoxycarbonyl-C₁ -C₆ -alkyl, aryl-C₁ -C₆ -alkyl, pyridyl-C₁ -C₆ -alkyl, thienyl-C₁ -C₆ -alkyl, aryl-C₃ -C₆ -alkenyl or aryloxy-C₁ -C₆ -alkyl, it being possible for the aromatic, pyridyl, or thienyl ring to be substituted by one or more of the following: C₁ -C₄ -alkyl, C₁ -C₂ -haloalkyl, C₃ -C₆ -cycloalkyl, C₁ -C₄ -alkoxy; C₁ -C₂ -haloalkoxy, halogen, aryl or aryloxy,R² and R³ are identical or different and are hydrogen, C₁ -C₄ -alkyl, C₁ -C₂ -haloalkyl, C₁ -C₄ -alkoxy, C₁ -C₂ -haloalkoxy, halogen, cyano or nitro, R² is hydrogen, C₁ -C₆ -alkyl or aryl, it being possible for the aromatic ring to be substituted by one or more of the following: C₁ -C₄ -alkyl, C₁ -C₂ -haloalkyl, C₁ -C₄ -alkoxy, C₁ -C₂ -haloalkoxy, halogen, cyano or nitro, and x is CH or N.
 2. A fungicide containing an inert carrier and a fungicidally effective amount of a substituted oxime ether of the general formula I ##STR14## where R¹ is C₁ -C₆ -alkyl, C₃ -C₆ -alkenyl, C₃ -C₄ -alkynyl, C₁ -C₆ -haloalkyl, C₃ -C₆ -haloalkenyl, C₁ -C₄ -alkoxy-C₁ -C₆ -alkyl, C₃ -C₆ -cycloalkyl, C₃ -C₆ -cycloalkyl-C₁ -C₄ -alkyl, cyano-C₁ -C₆ -alkyl, C₁ -C₆ -alkoxycarbonyl-C₁ -C₆ -alkyl, aryl-C₁ -C₆ -alkyl, pyridyl-C₁ -C₆ -alkyl, thienyl-C₁ -C₆ -alkyl, aryl-C₃ -C₆ -alkenyl or aryloxy-C₁ -C₆ -alkyl, it being possible for the aromatic, pyridyl, or thienyl ring to be substituted by one or more of the following: C₁ -C₄ -alkyl, C₁ -C₂ -haloalkyl, C₃ -C₆ -cycloalkyl, C₁ -C₄ -alkoxy; C₁ -C₂ -haloalkoxy, halogen, aryl or aryloxy,R² and R³ are identical or different and are hydrogen, C₁ -C₄ -alkyl, C₁ -C₂ -haloalkyl, C₁ -C₄ -alkoxy, C₁ -C₂ -haloalkoxy, halogen, cyano or nitro, R⁴ is hydrogen, C₁ -C₆ -alkyl or aryl, it being possible for the aromatic ring to be substituted by one or more of the following: C₁ -C₄ -alkyl, C₁ -C₂ -haloalkyl, C₁ -C₄ -alkoxy, C₁ -C₂ -haloalkoxy, halogen, cyano or nitro, and x is CH or N.
 3. A compound of the formula I as set forth in claim 1, where R¹ is ethyl, R² and R³ are hydrogen, R⁴ is methyl and X is CH, the oxime ether radical being in the 3-position on the phenyl radical.
 4. A compound of the formula I as set forth in claim 1, where R¹ is ethyl, R² and R³ are hydrogen, R⁴ is methyl and X is N, the oxime ether radical being in the 3-position on the phenyl radical.
 5. A compound of the formula I as set forth in claim 1, where R¹ is methyl, R², R³ and R⁴ are hydrogen and X is CH, the oxime ether radical being in the 3-position on the phenyl radical.
 6. A compound of the formula I as set forth in claim 1, where R¹ is methyl, R², R³ and R⁴ are hydrogen and X is CH, the oxime ether radical being in the 4-position on the phenyl radical. 